Pesticidal 1-polyarylpyrazoles

ABSTRACT

A compound of formula (I): compositions containing them and methods of use to control pests.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the priority of U.S. Provisional Patent Application No. 60/030,128, filed Nov. 4, 1996, incorporated by reference herein in its entirety and relied upon.

The invention relates to new 1-arylpyrazoles and derivatives thereof which have some valuable properties either as pesticides or as intermediates to make other pesticides. The invention further pertains to compositions of said compounds and methods, using said compounds either as intermediates to make other pesticides, or for the control of pests particularly insects, in particular to the application of said compounds or compositions in agricultural methods of use or for animal protection, particularly as pesticides, for controlling arthropods.

International Patent Publication No. WO 87/03781 and European Patent Publication No. 295117, 154115, 201852 describe insecticidal 1-(substituted phenyl)pyrazoles. Other prior art is also found in the text of these patent applications or the patents issued therefrom.

International Patent Publications No. WO 93/06089 and WO 94/21606 also describe insecticidal 1-(4-SF₅ substituted phenyl) heterocycles which may be pyrroles as well as imidazoles or pyrazoles. The teaching of these patents is not substantially different from International Patent Publication No. WO 87/03781 or from European Patent Publication No. 0295117 as far as pyrazoles are concerned.

It is an object of the present invention to provide new pesticidal compounds of the 1-arylpyrazole family together with processes for their preparation.

Another object of the present invention is to provide pesticidal compositions and pesticidal methods of use of the pesticidal pyrazole compounds against arthropods, especially insects, particularly in agricultural or horticultural crops, forestry, veterinary medicine or livestock husbandry, or in public health.

A third object of the present invention is to provide very active compounds with broad spectrum pesticidal activity, as well as compounds with selective special activity, e.g., aphicidal, miticidal, foliar insecticidal, soil insecticidal, systemic, antifeeding or pesticidal activity via seed treatment.

A fourth object of the present invention is to provide compounds with substantially enhanced and more rapid activity, especially against insects and more particularly insects in their larval stages.

A fifth objective of the present invention is to provide compounds with greatly improved (faster and greater) penetration into pest species when topically applied and to thus provide enhanced movement of the compounds to the pesticidal site(s) of action within the pest.

These and other objectives of the invention are met in whole or part and shall become readily apparent from the description of the present invention which follows.

The invention thus relates to compounds having the general formula (I): ##STR1## wherein: X is N or C--R₂ ;

Y is N or C--R₃ ;

W is N or C--R₄ ;

R₂ and R₃ are independently selected from H, halogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, haloalkoxy, CN, NO₂, --S(O)_(n) R₈, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, hydroxycarbonyl, aminosulfonyl, alkylaminosulfonyl, and dialkylaminosulfonyl;

R₄ is H, halogen, alkyl, alkoxy, CN, NO₂, haloalkyl, haloalkoxy, thiocyanato, formyl, alkylcarbonyl, --CH═N--OH, --CH═N--O-alkyl. --S(NH₂)(═NH), --S(O)_(n) R₈, mercapto, haloalkylcarbonyl, or a --S-- radical so that two molecules are bound together to form a disufide compound;

R₅ is hydrogen, halogen, --NR₉ R₁₀, --N═CR₁₁ R₁₉, --S(O)_(n) R₈, formyl, alkylcarbonyl, haloalkylcarbonyl, cyano, alkyl, haloalkyl, hydrazino, alkoxycarbonyl, alkylthiocarbonyl, 1H-pyrrol-1-yl or 1H-pyrazol-1-yl;

R₈ is alkyl or haloalkyl, alkenyl or alkynyl, or a cycloalkyl ring containing 3 to 5 carbon atoms;

R₁₁ is H, or alkyl;

R₁₉ may also be hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino, monoalkylamino, dialkylamino, or R₁₉ is phenyl, thienyl, pyridyl or furyl, each of which is unsubstituted or substituted with alkyl, haloalkyl, halogen, NO₂, CN, alkoxy, haloalkoxy, OH, alkylcarbonyl, alkylcarbonyloxy;

R₉ and R₁₀ independent of one another, are H, alkyl, haloalkyl, alkylcarbonyl, haloalkylcarbonyl, R₈ S(O)_(n), formyl, alkenyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl, aroyl; or are joined so as together form a divalent radical having 4 to 6 atoms in the chain, this divalent radical being alkylene, alkyleneoxyalkylene or alkyleneaminoalkylene, preferably to form a morpholine, pyrrolidine, piperidine or piperazine ring; the alkyl portion of R₉ and R₁₀ may be substituted by R₇ ;

R₇ is cyano, nitro, alkoxy, haloalkoxy, R₈ S(O)_(n), --C(O)alkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, --CO₂ H, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl;

Z is N or C--R₁₆ ;

R₁₂, R₁₃, R₁₅, R₁₆, are independently selected from hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, haloalkylsulfenyl, haloalkylsulfinyl, haloalkylsulfonyl, formyl, alkylcarbonyl, alkoxycarbonyl;

R₂₂, R₂₃, R₂₄, R₂₅, R₂₆ are halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, haloalkylcarbonyl, formyl, alkylcarbonyl, thioamide, amide, and alkoxycarbonyl, SF₅, R₈ S(O)_(n) ; preferably R₂₄ is halogen, haloalkyl or haloalkoxy; or R₂₂ and R₂₃ or R₂₃ and R₂₄ or R₂₅ and R₂₆ may also be together a divinylidene group (--CH═CH--CH═CH--) or a methylene diether (--O--CH₂ --O--) or halomethylene diether (--O--CF₂ --O--), so as to form a cyclic ring vicinal to the phenyl ring; or pesticidally acceptable salts thereof.

By the term "pesticidally acceptable salts" is meant salts the anions and cations of which are known and accepted in the art for the formation of pesticidally acceptable salts. Preferably such salts are water soluble. Suitable acid addition salts formed from compounds of formula (I) containing an amine group, include salts with inorganic acids for example hydrochlorides, phosphates, sulfates and nitrates, and salts with organic acids for example acetates. Suitable salts with bases formed from compounds of formula (I) containing a suitably acidic group include alkali metal (for example sodium or potassium) salts, ammonium salts and organic amine (for example diethanolamine or morpholine) salts.

In the present invention, some words are used in a specific sense:

The term "lower alkyl-S(O)_(n) " means a radical of the formula --S(O)_(n) -- lower alkyl. The term "R₁₀ S(O)_(n) " means a radical of the formula --S(O)_(n) R₁₀. The term "aminocarbonyl" means a carbamoyl radical, that is, a radical of the formula --C(O)NH₂. Similarly, the term "alkylaminocarbonyl" means an alkylcarbomoyl radical, that is, a radical of the formula --C(O)--NH-alkyl; and the term "dialkylaminocarbonyl" means a dialkylcarbamoyl radical, that is, a radical of the formula --C(O)--N(alkyl)₂ in which the alkyl moieties can be the same or different. The term "aminosulfonyl" means a sulfamoyl radical, that is, --SO₂ NH₂. Similarly, the term "alkylaminosulfonyl" means an alkylsulfamoyl radical, that is, a radical of the formula --SO₂ NH-alkyl; while the term "dialkylaminosulfonyl" means a dialkylsulfamoyl radical, which has the formula --SO₂ N(alkyl)₂ wherein the alkyl moieties can be the same or different.

The term "halo" before the name of a radical means that this radical is partially or completely halogenated, that is to say, substituted by F, Cl, Br, or I, in any combination, preferably by F or Cl. The term "halogen" means F, Cl, Br or I. The term "lower" before the name of a radical having a carbon skeleton means that this carbon skeleton has less than 6 carbon atoms. When the name of any substituent is repeated, it keeps the same meaning unless otherwise specified. The term "aryl" designates a carbon and/or heteroatom-containing aromatic radical which is preferably phenyl optionally substituted with one or more substituents selected from halogen, methyl and methoxy, especially phenyl, halophenyl, tolyl or xylyl. The term "aroyl" designates a carbonyl aromatic radical, that is, aryl-C(O)--, which is preferably a benzoyl, methylbenzoyl, halobenzoyl or xylylcarbonyl radical. The term "acyl" designates an alkylcarbonyl radical. The various individual radicals (such as alkyl, alkenyl, alkynyl, alkoxy and alkylene or the like) generally contain up to six carbon atoms.

A preferred class of compounds of formula (I) is that wherein

X is N;

Y is C--R₃ ;

W is C--R₄ ;

R₃ is H, halogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, haloalkoxy, CN, NO₂, --S(O)_(n) R₈, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, hydroxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl;

R₄ is H, halogen, alkyl, alkoxy, CN, NO₂, haloalkyl, haloalkoxy, thiocyanato, formyl, alkylcarbonyl, --CH═N--OH, --CH═N--O-alkyl, --S(NH₂)(═NH), --S(O)_(n) R₈, mercapto, haloalkylcarbonyl, or a --S-- radical so that two molecules are bound together to form a disufide compound;

R₅ is hydrogen, halogen, --NR₉ R₁₀, --N═CR₁₁ R₁₉, --S(O)_(n) R₈, formyl, alkylcarbonyl, haloalkylcarbonyl, cyano, lower alkyl, hydrazino, alkoxycarbonyl, alkylthiocarbonyl, 1H-pyrrol-1-yl or 1H-pyrazol-1-yl, preferably, amino --NR₉ R₁₀ ;

R₈ is alkyl or haloalkyl, alkenyl or alkynyl; or a cycloalkyl ring containing 3 to 5 carbon atoms; preferably R₈ is lower alkyl;

R₁₁ is H or alkyl;

R₁₉ may also be hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino, monoalkylamino, dialkylamino; or R₁₉ is phenyl, thienyl, pyridyl or furyl, all of them being optionally substituted with alkyl, haloalkyl, halogen, NO₂, CN, alkoxy, haloalkoxy, OH, alkylcarbonyl, alkylcarbonyloxy;

R₉ and R₁₀ are H, alkyl, haloalkyl, alkylcarbonyl, haloalkylcarbonyl, R₈ --S(O)_(n), formyl, alkenyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl, aroyl; or are joined so as together form a divalent radical having 4 to 6 atoms in the chain, this divalent radical being alkylene, alkyleneoxyalkylene or alkyleneaminoalkylene, preferably to form a morpholine, pyrrolidine, piperidine or piperazine ring; the alkyl portion of R₉ and R₁₀ may be substituted by R₇ ;

R₇ is cyano, nitro, alkoxy, haloalkoxy, R₈ S(O)_(n), --C(O)alkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, --CO₂ H, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl;

Z is N or C--R₁₆ ;

R₁₂, R₁₃, R₁₅, R₁₆, are separately hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, haloalkylsulfenyl, haloalkylsulfinyl, haloalkylsulfonyl, formyl, alkylcarbonyl, alkoxycarbonyl;

R₂₂, R₂₃, R₂₄, R₂₅, R₂₆ are halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, haloalkylcarbonyl, formyl, alkylcarbonyl, thioamide, amide, and alkoxycarbonyl, SF₅, R₈ S(O)_(n), preferably, R₂₄ is halogen, haloalkyl or haloalkoxy; or R₂₂ and R₂₃ or R₂₃ and R₂₄ or R₂₅ and R₂₆ may also be together a divinylidene-group (--CH═CH--CH═CH--) or a methylene diether (--O--CH₂ --O--) or halomethylene diether (--O--CF₂ --O--) so as to form a cyclic ring vicinal to the phenyl ring; or a pesticidally acceptable salt thereof.

Another preferred class of the compounds of formula (I) are those with one or more of the following features wherein:

X is N or C--R₂ ;

Y is N or C--R₃ ;

W is N or C--R₄ ;

R₃ is CN or halogen;

R₄ is H, halogen, formyl, or --S(O)_(n) R₈ ;

R₅ is hydrogen, halogen, C₁ -C₃ alkyl, C₁ -C₃ haloalkyl, or --NR₉ R₁₀ ;

R₈ is methyl, ethyl, --CF₃, --CFCl₂, --CF₂ Cl;

R₁₂ and R₁₆ are independently selected from F, Cl, Br and H;

R₁₃ and R₁₅ are H;

R₂₄ is --CF₃, --OCF₃, --CHF₂, --S(O)_(n) CF₃, --CFCl₂, --CF₂ Cl, --OCF₂ Cl, --OCFCl₂, Cl, Br or F; or

Z is CCl, CF, CBr or N.

A further especially preferred class of compounds are those wherein:

X is N;

Y is C--R₃ ;

W is C--R₄ ;

R₁₂ and R₁₆ are Cl or Br;

R₁₃ and R₁₅ are H;

R₂₄ is --CF₃, --OCF₃ or Br;

R₅ is amino;

R₉ and R₁₀ are H, alkyl or alkylcarbonyl;

R₈ is methyl or ethyl or CF₃, CCl₂ F, CClF₂ ; and

R₃ is CN or halogen.

For the above preferred compounds, there are optimum combinations of substituent groups.

Further, preferred S(O)_(n) R₈ substituents in formula (I) are: methylthio, methylsulfinyl, methylsulfonyl, ethylsulfinyl, ethylsulfonyl, ethylthio, cyclopropylsulfinyl, cyclopropylthio, cyclopropylsulfonyl, isopropylsulfinyl, isopropylsulfonyl, isopropylthio, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, dichlorofluoromethylthio, dichloromethylsulfinyl, dichloromethylsulfonyl, chlorodifluoromethylthio, chlorodifluoromethylsulfonyl or chlorodifluoromethylsulfinyl.

Some compounds are useful as intermediates to make other pesticides, others are useful directly as pesticides. Compounds wherein R₂₃ or R₂₄ or R₂₅ is formyl are preferred as intermediates as well as compounds wherein R₅ is H or compounds wherein simultaneously R₄ is not halogenated and R₂₂ and R₂₃ and R₂₄ and R₂₅ and R₂₆ are H.

The compounds of general formula (I) can be prepared by the application or adaptation of known methods (i.e., methods heretofore used or described in the chemical literature including the Chemical Abstracts) employing as starting material the compounds of formula (II) ##STR2## wherein the various substituents have the same meaning as in formula (I) and halo is a halogen atom, preferably bromine or iodine.

The compounds of formula (II) can be prepared by methods or processes similar to those described in International patent applications WO 87/03781, 93/06089, 94/21606, in European patent applications 295117, 403300, 385809, 0500209, 679650, 285,893, and 780,381, U.S. Pat. Nos. 5,232,940, 5,236,938, 5,187,185, 5,223,525 and German Patent application 19511269 or by other methods known to the skilled addressee. The skilled addressee understands and is generally knowledgeable of Chemical Abstracts.

According to a first method of preparation of compounds of formula (I) from compounds of formula (II), a compound of formula (II) is caused to react with a boric acid or ester, preferably in presence of a coupling catalyst, so as to form a compound of formula (III) ##STR3## wherein the substituents have the same meaning as previously indicated, and B(OR₃₀)₂ represents a boric acid or ester group (R₃₀ is preferably hydrogen, alkyl, or a divalent lower alkylene radical such that two R₃₀ O radicals may form a cyclic borate ester),

said compound (III) being, in a second step, caused to react with a compound of formula (VI) ##STR4## wherein R₂₀ is bromine or iodine or O--SO₂ CF₃.

The first step of this first process is generally and preferably conducted in an organic solvent, for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether; the temperature is generally between 50° C. and 150° C.; utilizing as catalysts organic derivatives of palladium including palladium acetate, tetrakis(triphenylphosphine)palladium(0) or Pd₂ (dibenzylidene acetone)₃, generally in the presence of a base such as an alkaline hydroxide or carbonate acetate ion or an amine. The boron derivative used as a reactant with the compound of formula (II) is preferably a cyclic diboron ester or acid of formula (R₃₀ O)₂ B--B(OR₃₀)₂.

The second step of this first process is advantageously conducted in an organic solvent, for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether; the temperature is generally between 50° C. and 150° C.; utilizing as catalysts organic derivatives of palladium including palladium acetate, tetrakis(triphenylphosphine)palladium(0) or Pd₂ (dibenzylidene acetone)₃, generally in the presence of a base such as an alkaline hydroxide or carbonate acetate ion or an amine.

According to another method of preparation of compound of formula (I), a compound of formula (II) is caused to react with a compound of formula (IV): ##STR5## wherein the substituents have the same meaning as previously indicated.

The process is generally and preferably conducted in an organic solvent, for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether: the temperature is generally between 50° C. and 150° C.; utilizing as catalysts organic derivatives of palladium including palladium acetate, tetrakis(triphenylphosphine)palladium(0) or Pd₂ (dibenzylidene acetone)₃, generally in the presence of a base such as an alkaline hydroxide or carbonate acetate ion or an amine.

According to still another method of preparation of compound of formula (I), a compound of formula (II) is caused to react in the presence of a catalyst as described above, with a hexaalkylstannane (alkyl or cycloalkyl)₃ Sn!₂ so as to form a compound of formula (V): ##STR6## which in a second step is caused to react with a compound of formula (IV) in the presence of a coupling catalyst.

The first step of the process is generally conducted in an organic solvent, for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether; at a temperature generally between 50° C. and 150° C.; utilizing as catalysts organic derivatives of palladium including palladium acetate, tetrakis(triphenylphosphine)palladium(0) or Pd₂ (dibenzylidene acetone)₃.

The second step of this second process is generally conducted in an organic solvent, for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether; the temperature is generally between 50° C. and 150° C.; as catalysts, organic derivatives of palladium such as Pd(P-phenyl₃)₄, Pd₂ (dibenzylidene acetone)₃, Pd(O--CO--CH₃)₂ may be cited.

According to still another method of preparation of compound of formula (I), a compound of formula (II) is caused to react with a compound of formula (VII) ##STR7## preferably in the presence of a coupling catalyst as described above, and preferably in a solvent as described above, and preferably at a temperature from 50° C. to 150° C.

According to another method of preparation of a compound of formula (I), a compound of formula (VIII): ##STR8## is reacted in a step to form a pyrrole, imidazole, triazole, or pyrazole of formula (I). Such reactions are known and can be found in Katritzky, Rees, and Scriven, Comprehensive Heterocyclic Chemistry II, volumes 2,3,4 1996, Pergamon Press, London.

The invention is illustrated by the following examples, which are not considered as limiting the invention but are given to better enable use of it.

EXAMPLE 1 Preparation of 1- 2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl!-3-cyano-4-trifluoromethylthio-5-aminopyrazole

A mixture of 6 g of 5-amino-3-cyano-1-(2,6-dichloro-4-bromophenyl)4-trifluoromethylthiopyrazole (prepared according to procedures reported in U.S. Pat. No. 5,232,940), 4-trifluoromethylphenylboronic acid (5.3 g), K₂ CO₃ (5.8 g), tris(dibenzylidene acetone)dipalladium (0.6 g) and diglyme was heated at 130° C. for 25 hours. After cooling to 20° C., the mixture was poured into water and extracted with diethyl ether. The ether solutions were combined, dried, filtered and the filtrate concentrated and purified by chromatography. The desired product as a solid (3.9 g, mp 181-184° C.) was obtained.

EXAMPLE 2 Preparation of 1- 2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl!-3-cyano-4-trifluoromethylsulfonyl-5-aminopyrazole

A solution of 1- 2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl!-3-cyano-4-trifluoromethylthio-5-aminopyrazole (0.5 g), m-chloroperbenzoic acid (2.2 g) and 1,2-dichloro-ethane was heated at reflux for 40 hours. After cooling to 20° C., the mixture was dissolved in diethyl ether and washed with sat. aqueous NaHCO₃ solution twice, then saturated aqueous NaHSO₃ solution twice, dried, filtered, and the filtrate concentrated and purified by chromatography. The desired product as a solid (0.13 g, mp 197-202° C.) was obtained.

EXAMPLE 3 Preparation of 1- 2,6-dichloro-4-(tributyltin)phenyl!-3-cyano-4-trifluoromethylthio-5-aminopyrazole

A mixture of 1-(2,6-dichloro-4-bromophenyl)-3-cyano-4-trifluoromethylthio-5-aminopyrazole (5 g), bis-(tributyltin) (6.7 g), tetrakis(tri-phenylphosphine)palladium(0) (1.3 g) and 1-methyl-2-pyrrolidinone was heated to reflux for 75 minutes, cooled to 20° C., poured to water and extracted with methyl t-butyl ether. After concentration to dryness, methylene chloride was added and stirred with saturated aqueous KF solution for 16 hours. More water was added and extracted with methylene chloride. The methylene chloride solutions were combined, dried, filtered and the filtrate concentrated and purified via chromatography. The desired product as a solid (1.9 g, mp 116-117° C.) was obtained.

EXAMPLE 4 Preparation of 1- 2,6-dichloro-4-(2,3,5,6-tetrafluoropyrid-4-yl)phenyl!-3-cyano-4-trifluoromethylthio-5-aminopyrazole

A mixture of 1- 2,6-dichloro-4-(tributyltin)phenyl!-3-cyano-4-trifluoromethylthio-5-aminopyrazole (0.5 g), 4-bromo-2,3,5,6-tetrafluoropyridine (0.1 mL), tetrakis(tri-phenylphosphine)palladium(0) (0.1 g) and THF was refluxed for 26 hours. After cooling to 20° C., methylene chloride was added and stirred with saturated aqueous KF solution for 16 hours. The mixture was filtered with diethyl ether and dried, filtered again and the filtrate concentrated and purified via chromatography. The desired product as a solid (87 mg, mp 100-104° C.) was obtained.

EXAMPLE 5 Preparation of 1- 2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl!-3-cyano-5-aminopyrazole

A mixture of 1-(2,6-dichloro-4-bromophenyl)-3-cyano-5-aminopyrazole (45 g, prepared according to procedures reported in U.S. Pat. No. 5,232,940), 4-trifluoromethylphenylboronic acid (45 g), 2M of Na₂ CO₃ (75 mL), tris(dibenzylideneacetone)dipalladium (6.4 g), toluene and ethanol was heated at 130° C. for 25 hours. After cooling to 20° C., the mixture was poured into water and extracted with diethyl ether. The ether solutions were combined, dried, filtered and the filtrate concentrated and purified via chromatography. The desired product as a solid (30.6 g, mp 195-199° C.) was obtained.

EXAMPLE 6 Preparation of 1- 2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl!-3-cyano-4-bromo-5-aminopyrazole

A mixture of 1- 2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl!-3-cyano-5-aminopyrazole (1 g), N-bromosuccinimide (0.5 g) and acetonitrile was stirred at 20° C. for 90 minutes, then concentrated and the residue was mixed with diethyl ether, washed with saturated aqueous NaHCO₃ solution, dried, filtered and the filtrate concentrated and purified via chromatography. The desired product as a solid (1.04 g, mp 178-180° C.) was obtained.

EXAMPLE 7 Preparation of 4-dichlorofluoromethylsulfenyl-1- 2-fluoro-4-(4-trifluoromethylphenyl)phenyl!imidazole

Step A

A solution of 4-bromo-2-fluoroaniline (3.8 g) in 20 ml of triethyl orthoformate was stirred at room temperature. After stirring for 1 h, tetrahydrofuran (40 ml), aminoacetonitrile hydrochloride (2.8 g), and diisopropylamine (5.3 ml) were added and stirring continued for an additional hour. After 1 h, the mixture was poured into 150 ml of ice water and extracted with 150 ml of dichloromethane. The organic solution was washed twice with water and dried over magnesium sulfate. Evaporation of solvents afforded a light purple solid (3.1 g), which was washed with hexane and filtered.

The solid was dissolved in 40 ml of dichloromethane at reflux, cooled to room temperature, and treated with tetramethylguanidine (1.6 ml), added dropwise over twenty minutes. After stirring at room temperature overnight, the mixture was cooled in an ice/salt bath and dichlorofluoromethylsulfenyl chloride (1.5 ml) was added. After 1 h, the mixture was diluted with 100 ml of methylene chloride and washed with saturated sodium bicarbonate solution, then with water, then dried over magnesium sulfate. After filtration and evaporation, chromatography on silica gel afforded 5-amino-4-dichlorofluoromethylsulfenyl-1-(2-fluoro-4-bromophenyl)imidazole (1.285 g).

Step B

1 g of 5-amino-4-dichlorofluoromethylsulfenyl-1-(2-fluoro-4-bromophenyl)imidazole was dissolved in 15 ml of tetrahydrofuran, cooled to 0° C., and treated with t-butylnitrite. After 1 h, the mixture is evaporated. Silca gel chromatography afforded 4-dichlorofluoromethylsulfenyl-1-(2-fluoro-4-bromophenyl)imidazole (0.555 g).

Step C

50 mg of 4-dichlorofluoromethylsulfenyl-1-(2-fluoro-4-bromophenyl)imidazole and 37 mg of trifluoromethylphenylboronic acid in 3 ml of toluene were treated with 0.13 ml of 2M aqueous potassium carbonate and a catalytic amount (about 5 mg) of palladium tetrakis(triphenylphoshine). The mixture was heated at 90° C. for 12 h, then cooled to room temperature and evaporated. Silica gel chromatography afforded 4-dichlorofluoromethylsulfenyl-1- 2-fluoro-4-(4-trifluoromethylphenyl)phenyl!imidazole (27.3 mg, mass spec m/e 438).

In a manner similar to that employed in examples 1 to 7, the following compounds in Tables 1-4 were also prepared. The last column of the table indicates the physical characteristic of the compound obtained from the mass spectrum analysis. It is the m/e value from the mass spectrum of the molecular ion. The number of the compound is for identification only.

N/A=Not Applicable

AroCH is 4-OH 3-methoxy phenyl!-CH, so that AroCH═N-- is the group 4-OH3-methoxy

                                      TABLE 1     __________________________________________________________________________     1 #STR9##     CMP. NO          R12             R13                R15 R16                       R22 R23 R24   R25                                        R26 R3  R4      R5      m/e     __________________________________________________________________________      1   Cl H  H   Cl (CH═CH)2                               H     H  H   CN  SCF3    NH2     478      2   Cl H  H   Cl H   H   H     H  H   CN  SCF3    NH2     428      3   Cl H  H   Cl Me  H   H     H  H   CN  SCF3    NH2     442      4   Cl H  H   Cl H   NH2 H     H  H   CN  SCF3    NH2     443      5   Cl H  H   Cl H   NO2 H     H  H   CN  SCF3    NH2     473      6   Cl H  H   Cl H   NHAc                               H     H  H   CN  SCF3    NH2     485      7   Cl H  H   Cl H   CHO H     H  H   CN  SCF3    NH2     456      8   Cl H  H   Cl H   H   OMe   H  H   CN  SCF3    NH2     458      9   Cl H  H   Cl H   H   SMe   H  H   CN  SCF3    NH2     474      10  Cl H  H   Cl H   H   F     H  H   CN  SCF3    NH2     446      11  Cl H  H   Cl H   F   H     H  H   CN  SCF3    NH2     446      12  Cl H  H   Cl H   Cl  F     H  H   CN  SCF3    NH2     480      13  Cl H  H   Cl H   H   Cl    H  H   CN  SCF3    NH2     462      14  Cl H  H   Cl H   H   Br    H  H   CN  SCF3    NH2     506      15  Cl H  H   Cl H   Cl  H     Cl H   CN  SCF3    NH2     496      16  Cl H  H   Cl H   H   CF3   H  H   CN  SCF3    NH2     496      17  Cl H  H   Cl H   CF3 H     CF3                                        H   CN  SCF3    NH2     564      18  Cl H  H   Cl (CH═CH)2                               H     H  H   CN  SMe     NH2     424      19  Cl H  H   Cl H   H   H     H  H   CN  SMe     NH2     374      20  Cl H  H   Cl Me  H   H     H  H   CN  SMe     NH2     388      21  Cl H  H   Cl H   NH2 H     H  H   CN  SMe     NH2     389      22  Cl H  H   Cl H   NO2 H     H  H   CN  SMe     NH2     419      23  Cl H  H   Cl H   NHAc                               H     H  H   CN  SMe     NH2     431      24  Cl H  H   Cl H   H   CHO   H  H   CN  SMe     NH2     402      25  Cl H  H   Cl H   H   OMe   H  H   CN  SMe     NH2     404      26  Cl H  H   Cl H   F   H     H  H   CN  SMe     NH2     392      27  Cl H  H   Cl H   Cl  F     H  H   CN  SMe     NH2     426      28  Cl H  H   Cl Cl  H   Cl    H  H   CN  SMe     NH2     442      29  Cl H  H   Cl H   H   CF3   H  H   CN  SMe     NH2     442      30  Cl H  H   Cl H   CF3 H     CF3                                        H   CN  SMe     NH2     510      31  Cl H  H   Cl H   Br  H     H  H   CN  SMe     NH2     452      32  Cl H  H   Cl Me  H   H     H  H   CN  SCF3    Van-CH═N--                                                                576      33  Cl H  H   Cl H   NO2 H     H  H   CN  SCF3    Van-CH═N--                                                                607      34  Cl H  H   Cl H   NHAc                               H     H  H   CN  SCF3    Van-CH═N--                                                                619      35  Cl H  H   Cl H   H   CHO   H  H   CN  SCF3    Van-CH═N--                                                                590      36  Cl H  H   Cl H   H   OMe   H  H   CN  SCF3    Van-CH═N--                                                                592      37  Cl H  H   Cl H   Cl  F     H  H   CN  SCF3    Van-CH═N--                                                                614      38  Cl H  H   Cl Cl  H   Cl    H  H   CN  SCF3    Van-CH═N--                                                                630      39  Cl H  H   Cl H   H   CF3   H  H   CN  SCF3    Van-CH═N--                                                                630      40  Cl H  H   Cl H   H   CF3   H  H   CN  S(O)2CCl2F                                                        NH2     560      41  Cl H  H   Cl H   H   CF3   H  H   CN  S(O)2CCl2F                                                        NH2     544      42  Cl H  H   Cl H   H   CF3   H  H   CN  SCCl2F  NH2     528      43  Cl H  H   Cl H   H   CF3   H  H   CN  SOCF3   NH2     512      44  Cl H  H   Cl H   H   CF3   H  H   CN  S(O)2CF3                                                        NH2     528      45  Cl H  H   Cl H   H   CF3   H  H   PhC(O)                                                SCF3    NH2     575      46  Cl H  H   Cl (CH═CH)2                               H     H  H   CN  SCF3    H       463      47  Cl H  H   Cl H   (CH═)2                                     H  H   CN  SCF3    H       463      48  Cl H  H   Cl H   H   H     H  H   CN  SCF3    H       413      49  Cl H  H   Cl H   NO2 H     H  H   CN  SCF3    H       458      50  Cl H  H   Cl H   H   OMe   H  H   CN  SCF3    H       443      51  Cl H  H   Cl H   H   SMe   H  H   CN  SCF3    H       459      52  Cl H  H   Cl H   H   F     H  H   CN  SCF3    H       431      53  Cl H  H   Cl H   F   H     H  H   CN  SCF3    H       431      54  Cl H  H   Cl H   Cl  F     H  H   CN  SCF3    H       465      55  Cl H  H   Cl H   H   Cl    H  H   CN  SCF3    H       447      56  Cl H  H   Cl H   H   Br    H  H   CN  SCF3    H       491      57  Cl H  H   Cl H   Cl  H     Cl H   CN  SCF3    H       481      58  Cl H  H   Cl Cl  H   Cl    H  H   CN  SCF3    H       481      59  Cl H  H   Cl H   H   CF3   H  H   CN  SCF3    H       481      60  Cl H  H   Cl H   CF3 H     H  H   CN  SCF3    H       481      61  Cl H  H   Cl H   CF3 H     CF3                                        H   CN  SCF3    H       549      62  Cl H  H   Cl H   Cl  H     H  H   CN  SCF3    H       447      63  Cl H  H   Cl H   Br  H     H  H   CN  SCF3    NH2     491      64  Cl H  H   Cl H   H   CF3   H  H   PhC(O)                                                S(O)2CCl2F                                                        NH2     639      65  Cl H  H   Cl H   H   Br    H  H   CN  SCCl2F  NH2     538      66  Cl H  H   Cl Cl  H   CF3   H  Cl  CN  SCF3    NH2     564      67  Cl H  H   Cl H   H   OCF3  H  H   CN  SCF3    NH2     512      68  Cl H  H   Cl H   H   CF3   H  H   PhC(O)                                                S(O)2CClF2                                                        NH2     623      69  Cl H  H   Cl H   H   CF3   H  H   CN  H       NH2     396      70  Cl H  H   Cl H   H   CF3   H  H   CN  Br      NH2     474      71  Cl H  H   Cl H   H   CF3   H  H   CN  SEt     NH2     456      72  Cl H  H   Cl H   H   CF3   H  H   CN  SMe     NH2     442      73  Cl H  H   Cl H   H   CF3   H  H   CN  SCN     NH2     453      74  Cl H  H   Cl H   H   CF3   H  H   CN  Cl      NH2     430      75  Cl H  H   Cl H   H   CF3   H  H   CN  SOMe    NH2     458      76  Cl H  H   Cl H   H   CF3   H  H   CN  S(O)Et  NH2     472      77  Cl H  H   Cl H   H   Br    H  H   CN  S(O)2CCl2F                                                        NH2     570      78  Cl H  H   Cl H   H   CF3   H  H   CN  S(O)2CH3                                                        NH2     474      79  Cl H  H   Cl H   H   CF3   H  H   CN  S(O)2Et NH2     488      80  Cl H  H   Cl H   H   CF3   H  H   CONH2                                                C(OH)(CF3)2                                                        NH2     580      81  Cl H  H   Cl H   H   CF3   H  H   CN  C(OH)(CF3)2                                                        NH2     562      82  Cl H  H   Cl H   H   CF3   H  H   CN  H       NHAc    438      83  Cl H  H   Cl H   H   CF3   H  H   Ac  SMe     NH2     459      84  Cl H  H   Cl H   H   CF3   H  H   CN  CF(CF3)2                                                        NH2     564      85  Cl H  H   Cl H   H   CF3   H  H   CN  SCCl2F  H       513      86  Cl H  H   Cl H   H   CF3   H  H   CN  S(O)2CCl2F                                                        H       545      87  Cl H  H   Cl H   Cl  Cl    H  H   CN  H       NH2     396      88  Cl H  H   Cl H   H   OCF3  H  H   CN  H       NH2     412      89  Cl H  H   Cl H   H   H     H  H   CN  H       NH2     346      90  Cl H  H   Cl H   H   CO2Me H  H   CN  H       NH2     386      91  Cl H  H   Cl H   Cl  Cl    H  H   CN  SCF3    NH2     496      92  Cl H  H   Cl F   H   H     H  H   CN  SCF3    NH2     446      93  Cl H  H   Cl H   H   CO2Me H  H   CN  SCF3    NH2     486      94  Cl H  H   Cl H   H   CF3   H  H   CN  SCCl2F  Br      591      95  Cl H  H   Cl H   H   CF3   H  H   Ac  S(O)2CH3                                                        NH2     491      96  Cl H  H   Cl Cl  H   H     H  Cl  CN  SCF3    NH2     496      97  Cl H  H   Cl Cl  H   Cl    H  H   CN  SCF3    NH2     496      98  Cl H  H   Cl Cl  H   CF3   H  Cl  CN  SCF3    NH2     564      99  Cl H  H   Cl CF3 H   H     H  H   CN  SCF3    NH2     496     100  Cl H  H   Cl NO2 H   CF3   H  H   CN  SCF3    NH2     541     101  Cl H  H   Cl Me  H   F     H  H   CN  SCF3    NH2     460     102  Cl H  H   Cl H   F   H     F  H   CN  SCF3    NH2     464     103  Cl H  H   Cl F   H   H     H  F   CN  SCF3    NH2     464     104  Cl H  H   Cl H   OCF3                               H     H  H   CN  SCF3    NH2     512     105  Cl H  H   Cl H   H   H     Cl H   CN  SCF3    NH2     480     106  Cl H  H   Cl H   CN  H     H  H   CN  SCF3    NH2     453     107  Cl H  H   Cl H   OMe H     H  H   CN  SCF3    NH2     458     108  Cl H  H   Cl H   H   CH2CN H  H   CN  SCF3    NH2     467     109  Cl H  H   Cl H   H   Ms    H  H   CN  SCF3    NH2     506     110  Cl H  H   Cl H   H   SO2NH2                                     H  H   CN  SCF3    NH2     507     111  Cl H  H   Cl H   H   NMe2  H  H   CN  SCF3    NH2     471     112  Cl H  H   Cl OCH2O   H     H  H   CN  SCF3    NH2     472     113  Cl H  H   Cl H   H   CN    H  H   CN  SCF3    NH2     453     114  Cl H  H   Cl H   H   CN    H  H   CN  SCF3    NH2     453     115  Cl H  H   Cl F   H   F     H  H   CN  SCF3    NH2     464     116  Cl H  H   Cl H   H   CONH2 H  H   CN  SCF3    NH2     471     117  Cl H  H   Cl H   Cl  CN    H  H   CN  SCF3    NH2     487     118  Cl H  H   Cl H   CF3 H     H  H   CN  SCF3    NH2     496     119  Cl H  H   Cl F   F   F     F  F   CN  SCF3    NH2     518     120  Cl H  H   Cl H   H   OPh   H  H   CN  SCF3    NH2     520     121  Cl H  H   Cl Cl  H   CF3   H  H   CN  SCF3    NH2     530     122  Cl H  H   Cl H   OCF2O     H  H   CN  SCF3    NH2     508     123  Cl H  H   Cl H   F   NH2   H  H   CN  SCF3    NH2     461     124  Cl H  H   Cl H   CF3 NO2   H  H   CN  SCF3    NH2     541     125  Cl H  H   Cl OH  H   H     H  H   CN  SCF3    NH2     444     126  Cl H  H   Cl H   H   NH2   H  H   CN  SCF3    NH2     443     127  Cl H  H   Cl H   H   OH    H  H   CN  SCF3    NH2     444     128  Cl H  H   Cl H   CF3 H     NH2                                        NH2 CN  SCF3    NH2     526     129  Cl H  H   Cl H   F   Me    H  H   CN  SCF3    NH2     460     130  Cl H  H   Cl CN  F   H     H  H   CN  SCF3    NH2     471     131  Cl H  H   Cl H   Me  F     H  H   CN  SCF3    NH2     460     132  Cl H  H   Cl Me  H   H     F  H   CN  SCF3    NH2     460     133  Cl H  H   Cl Ph  H   H     H  H   CN  SCF3    NH2     504     134  Cl H  H   Cl OH  OMe H     CHO                                        H   CN  SCF3    NH2     502     135  Cl H  H   Cl H   Cl  Cl    H  H   CN  S(O)2CH3                                                        NH2     474     136  Cl H  H   Cl Cl  H   H     H  Cl  CN  S(O)2CH3                                                        NH2     474     137  Cl H  H   Cl Cl  H   Cl    H  H   CN  S(O)2CH3                                                        NH2     474     138  Cl H  H   Cl Cl  H   CF3   H  Cl  CN  S(O)2CH3                                                        NH2     542     139  Cl H  H   Cl H   H   OCF3  H  H   CN  S(O)2CH3                                                        NH2     490     140  Cl H  H   Cl CF3 H   H     H  H   CN  S(O)2CH3                                                        NH2     474     141  Cl H  H   Cl NO2 H   CF3   H  H   CN  S(O)2CH3                                                        NH2     519     142  Cl H  H   Cl Me  H   F     H  H   CN  S(O)2CH3                                                        NH2     438     143  Cl H  H   Cl H   F   H     F  H   CN  S(O)2CH3                                                        NH2     442     144  Cl H  H   Cl F   H   H     H  F   CN  S(O)2CH3                                                        NH2     442     145  Cl H  H   Cl F   H   H     H  H   CN  S(O)2CH3                                                        NH2     424     146  Cl H  H   Cl H   H   CF3   H  H   CN  C═NOH                                                        NH2     439     147  Cl H  H   Cl H   H   CF3   H  H   CN  NO2     NHAc    483     148  Cl H  H   Cl H   H   CF3   H  H   CN  NO2     NH2     441     149  Cl H  H   Cl F   H   F     H  H   CN  S(O)2CH3                                                        NH2     442     150  Cl H  H   Cl H   OCF3                               H     H  H   CN  S(O)2CH3                                                        NH2     490     151  Cl H  H   Cl H   F   H     Cl H   CN  S(O)2CH3                                                        NH2     458     152  Cl H  H   Cl H   H   CONH2 H  H   CN  S(O)2CH3                                                        NH2     449     153  Cl H  H   Cl H   CN  H     H  H   CN  S(O)2CH3                                                        NH2     431     154  Cl H  H   Cl H   H   SMe   H  H   CN  S(O)2CH3                                                        NH2     452     155  Cl H  H   Cl H   OMe H     H  H   CN  S(O)2CH3                                                        NH2     436     156  Cl H  H   Cl H   H   CH2CN H  H   CN  S(O)2CH3                                                        NH2     445     157  Cl H  H   Cl H   H   Ms    H  H   CN  S(O)2CH3                                                        NH2     484     158  Cl H  H   Cl H   H   SO2NH2                                     H  H   CN  S(O)2CH3                                                        NH2     485     159  Cl H  H   Cl H   H   NMe2  H  H   CN  S(O)2CH3                                                        NH2     449     160  Cl H  H   Cl OCH2O   H     H  H   CN  S(O)2CH3                                                        NH2     450     161  Cl H  H   Cl H   Cl  CN    H  H   CN  S(O)2CH3                                                        NH2     465     162  Cl H  H   Cl H   H   CN    H  H   CN  S(O)2CH3                                                        NH2     431     163  Cl H  H   Cl H   H   CO2Me H  H   CN  S(O)2CH3                                                        NH2     464     164  Cl H  H   Cl H   CF3 H     H  H   CN  S(O)2CH3                                                        NH2     474     165  Cl H  H   Cl F   F   F     F  F   CN  S(O)2CH3                                                        NH2     496     166  Cl H  H   Cl H   H   OPh   H  H   CN  S(O)2CH3                                                        NH2     498     167  Cl H  H   Cl Cl  H   CF3   H  H   CN  S(O)2CH3                                                        NH2     508     168  Cl H  H   Cl Cl  H   SF5   H  Cl  CN  S(O)2CH3                                                        NH2     600     169  Cl H  H   Cl Cl  H   OCF3  H  Cl  CN  S(O)2CH3                                                        NH2     558     170  Cl H  H   Cl H   OCF2O     H  H   CN  S(O)2CH3                                                        NH2     486     171  Cl H  H   Cl H   CO2H                               OH    H  H   CN  S(O)2CH3                                                        NH2     466     172  Cl H  H   Cl H   F   OH    H  H   CN  S(O)2CH3                                                        NH2     440     173  Cl H  H   Cl H   F   NH2   H  H   CN  S(O)2CH3                                                        NH2     439     174  Cl H  H   Cl H   CF3 NH2   H  H   CN  S(O)2CH3                                                        NH2     519     __________________________________________________________________________

                                      TABLE 2     __________________________________________________________________________     2 #STR10##     CMP. NO          R12             R13                R15                   R16                      R2                        R22                           R23 R24 R25                                      R26                                         R3    R4  R5                                                     m/e     __________________________________________________________________________     175  Cl H  H  Cl H (CH═CH)2                               H   H  H  SCFCl2                                               CN  Cl                                                     528     176  Cl H  H  Cl Cl                        H  (CH═CH2)                                   H  H  CN    SCFCl2                                                   H 528     177  Cl H  H  Cl Cl                        H  H   H   H  H  CN    SCFCl2                                                   H 478     178  Cl H  H  Cl H H  H   Me  H  H  SCFCl2                                               CN  Cl                                                     492     179  Cl H  H  Cl H Me H   H   H  H  SCFCl2                                               CN  Cl                                                     492     180  Cl H  H  Cl Cl                        H  NH2 H   H  H  CN    SCFCl2                                                   H 493     181  Cl H  H  Cl H H  NO2 H   H  H  SCFCl2                                               CN  Cl                                                     523     182  Cl H  H  Cl Cl                        H  NHAc                               H   H  H  CN    SCFCl2                                                   H 535     183  Cl H  H  Cl H CHO                           H   H   H  H  SCFCl2                                               CN  Cl                                                     506     184  Cl H  H  Cl H H  CHO H   H  H  SCFCl2                                               CN  Cl                                                     506     185  Cl H  H  Cl Cl                        H  H   CHO H  H  CN    SCFCl2                                                   H 506     186  Cl H  H  Cl H OMe                           H   H   H  H  SCFCl2                                               CN  Cl                                                     508     187  Cl H  H  Cl H H  OMe H   H  H  SCFCl2                                               CN  Cl                                                     508     188  Cl H  H  Cl Cl                        H  H   OMe H  H  CN    SCFCl2                                                   H 508     189  Cl H  H  Cl Cl                        H  H   SMe H  H  CN    SCFCl2                                                   H 524     190  Cl H  H  Cl H H  H   F   H  H  SCFCl2                                               CN  Cl                                                     496     191  Cl H  H  Cl Cl                        H  F   H   H  H  CN    SCFCl2                                                   H 496     192  Cl H  H  Cl Cl                        H  Cl  F   H  H  CN    SCFCl2                                                   H 530     193  Cl H  H  Cl H H  H   Cl  H  H  SCFCl2                                               CN  Cl                                                     512     194  Cl H  H  Cl H H  H   Br  H  H  SCFCl2                                               CN  Cl                                                     556     195  Cl H  H  Cl Cl                        H  Cl  H   Cl H  CN    SCFCl2                                                   H 546     196  Cl H  H  Cl H Cl H   Cl  H  H  SCFCl2                                               CN  Cl                                                     546     197  Cl H  H  Cl Cl                        H  H   CF3 H  H  CN    SCFCl2                                                   H 546     198  Cl H  H  Cl Cl                        H  CF3 H   H  H  CN    SCFCl2                                                   H 546     199  Cl H  H  Cl H H  CF3 H   CF3                                      H  SCFCl2                                               CN  Cl                                                     614     200  Cl H  H  Cl Cl                        H  Cl  H   H  H  CN    SCFCl2                                                   H 512     201  Cl H  H  Cl Cl                        H  Br  H   H  H  CN    SCFCl2                                                   H 556     202  Cl H  H  Cl H H  H   CF3 H  H  S(O)CFCl2                                               CN  Cl                                                     562     203  Cl H  H  Cl H H  H   CF3 H  H  S(O)CFCl2                                               CN  Cl                                                     578     204  H  H  H  H  H H  H   CF3 H  H  CHO   H   H 315     205  H  H  H  Me H H  H   CF3 H  H  CHO   H   H 329     206  Me H  H  Me H H  H   CF3 H  H  CHO   H   H 343     207  Cl H  H  H  H H  H   CF3 H  H  CHO   H   H 349     208  H  Cl H  H  H H  H   CF3 H  H  CHO   H   H 349     209  Cl H  H  Me H H  H   CF3 H  H  CHO   H   H 363     210  Cl H  H  Cl H H  H   CF3 H  H  CHO   H   H 383     211  F  H  H  H  H H  H   CF3 H  H  CHO   H   H 333     212  F  H  H  F  H H  H   CF3 H  H  CHO   H   H 351     213  H  H  H  CF3                      H H  H   CF3 H  H  CHO   H   H 383     214  H  H  CF3                   H  H H  H   CF3 H  H  CHO   H   H 383     215  F  F  F  F  H H  H   CF3 H  H  CHO   H   H 387     216  Me H  H  NO2                      H H  H   CF3 H  H  CHO   H   H 374     217  H  H  (CH═CH)2                      H H  H   CF3 H  H  CHO   H   H 365     __________________________________________________________________________

                                      TABLE 3     __________________________________________________________________________     3 #STR11##     CMP. NO          R12             R13                R15                   R16                      R22                         R23 R24                                R25                                   R26                                      R3    R5 m/3     __________________________________________________________________________     218  Cl H  H  Cl H  H   CF3                                H  H  t-Bu  NH2                                               428     219  Cl H  H  Cl H  H   CF3                                H  H  t-Bu  H  413     220  Cl H  H  Cl H  H   CF3                                H  H  t-Bu  Br 491     221  Cl H  H  Cl H  H   CF3                                H  H  CF3   NH2                                               440     222  Cl H  H  Cl H  NO2 H  H  H  CF3   NH2                                               417     223  Cl H  H  Cl H  F   H  H  H  CF3   NH2                                               390     224  Cl H  H  Cl H  H   CF3                                H  H  CF3   Br 503     225  Cl H  H  Cl H  H   CF3                                H  H  CF3   H  425     226  Cl H  H  Cl H  (CH═CH)2                                H  H  CF3   NH2                                               422     227  Cl H  H  Cl (CH═CH)2                             H  H  H  CF3   NH2                                               422     228  Cl H  H  Cl Me H   H  H  H  CF3   NH2                                               386     229  Cl H  H  Cl H  OMe H  H  H  CF3   NH2                                               402     230  Cl H  H  Cl H  H   OMe                                H  H  CF3   NH2                                               402     231  Cl H  H  Cl H  H   SMe                                H  H  CF3   NH2                                               418     232  Cl H  H  Cl H  H   F  H  H  CF3   NH2                                               390     233  Cl H  H  Cl H  H   Cl H  H  CF3   NH2                                               406     234  Cl H  H  Cl H  H   Br H  H  CF3   NH2                                               450     235  Cl H  H  Cl H  Cl  H  Cl H  CF3   NH2                                               440     236  Cl H  H  Cl Cl H   Cl H  H  CF3   NH2                                               440     237  Cl H  H  Cl H  CF3 H  H  H  CF3   NH2                                               440     238  Cl H  H  Cl H  Cl  H  H  H  CF3   NH2                                               406     239  Cl H  H  Cl H  Br  H  H  H  CF3   NH2                                               450     240  Cl H  H  Cl (CH═CH)2                             H  H  H  CF3   H  407     241  Cl H  H  Cl H  H   H  H  H  CF3   H  357     242  Cl H  H  Cl H  H   Me H  H  CF3   H  371     243  Cl H  H  Cl H  NO2 H  H  H  CF3   H  402     244  Cl H  H  Cl H  CHO H  H  H  CF3   H  385     245  Cl H  H  Cl H  OMe H  H  H  CF3   H  387     246  Cl H  H  Cl H  H   F  H  H  CF3   H  375     247  Cl H  H  Cl H  H   F  H  H  CF3   H  375     248  Cl H  H  Cl H  F   H  H  H  CF3   H  375     249  Cl H  H  Cl H  Cl  F  H  H  CF3   H  409     250  Cl H  H  Cl H  (CH═CH)2                                H  H  CF3   H  407     251  Cl H  H  Cl H  NHAc                             H  H  H  CF3   H  414     252  Cl H  H  Cl CHO                         H   H  H  H  CF3   H  385     253  Cl H  H  Cl H  H   CHO                                H  H  CF3   H  385     254  Cl H  H  Cl OMe                         H   H  H  H  CF3   H  387     255  Cl H  H  Cl H  H   CF3                                H  H  SMe   H  403     256  Cl H  H  Cl H  H   CF3                                H  H  SMe   NH2                                               418     257  Cl H  H  Cl H  H   CF3                                H  H  SOMe  NH2                                               434     258  Cl H  H  Cl H  H   CF3                                H  H  SOMe  H  419     259  Cl H  H  Cl H  H   CF3                                H  H  SOMe  Br 497     260  Cl H  H  Cl H  H   CF3                                H  H  SCCl2F                                            H  489     261  Cl H  H  Cl H  H   CF3                                H  H  S(O)CCl2F                                            H  505     263  Cl H  H  Cl H  H   CF3                                H  H  S(O)2CCl2F                                            H  521     __________________________________________________________________________

                                      TABLE 4     __________________________________________________________________________     4 #STR12##     CMP. NO          R12             R13                R15                   R16                      R21    R23 R24 R25                                        R26                                           R4    R5 m/e     __________________________________________________________________________     264  Cl H  H  Cl H      H   CF3 H  H  SCCl.sub.2 F                                                 H  488     265  Cl H  H  Cl H      H   CF3 H  H  SCCl.sub.2 F                                                 Br 566     266  Cl H  H  Cl H      H   CF3 H  H  SCCl.sub.2 F                                                 NH2                                                    503     267  Cl H  H  Cl H      H   CF3 H  H  SO.sub.2 CCl2F                                                 Br 537     268  Cl H  H  Cl H      H   CF3 H  H  SOCCl.sub.2 F                                                 H  504     269  Cl H  H  Cl H      H   CF3 H  H  SO2CCl2F                                                 H  520     270  Cl H  H  F  H      H   CF3 H  H  SOCCl2F                                                 H  454     271  Cl H  H  Cl Cl     H   CF3 H  H  SOCCl2F                                                 H  572     272  Cl H  H  Cl H      H   OCF3                                     H  H  SOCCl2F                                                 H  520     273  Cl H  H  Cl H      OCF2O   H  H  SOCCl2F                                                 H  516     274  Cl H  H  Cl H      H   H   H  H  SOCCl2F                                                 H  436     275  Cl H  H  Cl Me     H   Me  Me H  SOCCl2F                                                 H  478     276  Cl H  H  Cl Me     H   H   H  Me SOCCl2F                                                 H  464     277  Cl H  H  Cl H      H   t-Bu                                     H  H  SOCCl2F                                                 H  492     278  Cl H  H  Cl H      CF3 H   CF3                                        H  SOCCl2F                                                 H  572     279  Cl H  H  Cl H      CH2CN                                 H   H  H  SOCCl2F                                                 H  475     280  Cl H  H  Cl H      OCH2O   H  H  SOCCl2F                                                 H  480     281  Cl H  H  Cl H      F   F   H  H  SOCCl2F                                                 H  472     282  Cl H  H  Cl F      F   NH2 F  H  SOCCl2F                                                 H  523     283  Cl H  H  Cl NO2    H   CF3 H  H  SOCCl2F                                                 H  549     284  Cl H  H  Cl H      H   CH2CN                                     H  H  SOCCl2F                                                 H  475     285  Cl H  H  Cl H      H   n-Bu                                     H  H  SOCCl2F                                                 H  492     286  Cl H  H  Cl Cl     H   Cl  H  H  SOCCl2F                                                 H  504     287  Cl H  H  Cl H      NO2 NH2 Me Me SOCCl2F                                                 H  524     288  Cl H  H  Cl Cl     H   CF3 H  H  SOCCl2F                                                 H  538     289  Cl H  H  Cl Cl     H   Cl  H  Cl SOCCl2F                                                 H  538     290  Cl H  H  Cl F      F   CF3 F  F  SOCCl2F                                                 H  576     291  Cl H  H  Cl F      F   CN  F  F  SOCCl2F                                                 H  533     292  Cl H  H  Cl 5-tetrazolyl                             H   H   H  H  SOCCl2F                                                 H  504     293  Cl H  H  Cl H      H   CN  H  H  SOCCl2F                                                 H  461     294  Cl H  H  Cl Cl     H   SF5 H  Cl SOCCl2F                                                 H  630     295  H  H  H  F  H      H   CF3 H  H  SCCl2F                                                 H  438     296  Cl H  H  Cl H      H   CF3 H  H  SCF3  H  456     297  Cl H  H  Cl H      H   CF3 H  H  SOCF3 H  472     298  Cl H  H  Cl H      H   CF3 H  H  SO.sub.2 CF3                                                 H  488     __________________________________________________________________________

The present invention provides also a method for controlling pests at a locus comprising applying to said locus a pesticidally effective amount of a compound of formula (I), or a pesticidal composition comprising a pesticidally effective amount of a compound of formula (I) and a pesticidally acceptable carrier therefor. In a preferred embodiment, the invention provides a method for controlling insects at a locus comprising applying to said locus an insecticidally effective amount of a compound of formula (I), or an insecticidally effective amount of an insecticidal composition comprising an insecticidally effective amount of a compound of formula (I) and an agriculturally acceptable inert carrier therefor. Preferably, the locus to which the pesticidally (especially insecticidally) effective amount is applied is a crop-growing area, that is, an area in which a crop is growing or in which a crop has been planted, or an area in which a crop will be planted/grown.

The compositions which can be used in the invention for the pesticidal/insecticidal treatment of the invention can comprise from about 0.001 to 95% of the compound of formula (I).

The diluted liquid formulations, as applied to the locus to be treated or crop, generally comprise from about 0.001 to about 3% of active ingredient of formula (I), preferably from about 0.1 to about 0.5%.

The solid formulations as applied to the locus or crop generally comprise from about 0.1 to about 8% of active ingredient of formula (I), preferably from about 0.5 to about 1.5%.

The concentrated compositions are the compositions which are commercialized or transported or stored. For application to plants, they are normally diluted in water and applied in such diluted form. The diluted forms are part of the invention as well as the concentrated forms.

The concentrated formulations generally comprise from about 5 to about 95% of active ingredient of formula (I), preferably from about 10 to about 50%.

The insecticidal compositions of the invention can be applied once, or more than once, throughout the whole insect season. Insecticidal compositions according to the invention are usually applied to the locus to be treated or crop area at a rate of from about 0.01 to about 2 kg/ha of active ingredient, preferably from about 0.1 to about 1 kg/ha.

The concentrated insecticidal compositions according to the invention can be in the form of a solid, e.g., dusts or granules or wettable powders, or, preferably, in the form of a liquid, such as an emulsifiable concentrate or a true solution.

The compositions according to the instant invention generally comprise from about 0.5 to about 95% of active ingredient of formula (I). The remainder of the composition up to 100% comprises a carrier as well as various additives such as those hereafter indicated.

By "carrier", there is meant herein an organic or inorganic material, which can be natural or synthetic, and which is associated with the active ingredient and which facilitates its application to the locus to be treated or crop. This carrier is thus generally inert and should be agriculturally acceptable, especially on the contemplated or treated locus or crop. The carrier can be solid (clay, silicates, silica, resins, wax, fertilizers, etc.) or liquid (water, alcohols, ketones, oil solvents, saturated or unsaturated hydrocarbons, chlorinated hydrocarbons, liquified petroleum gas, etc.).

Among the many additives, the compositions of the invention can comprise surfactants as well as other ingredients such as dispersants, stickers, antifoam agents, antifreezing agents, dyestuffs, thickeners, adhesives, protective colloids, penetrating agents, stabilizing agents, sequestering agents, antiflocculating agents, corrosion inhibitors, pigments and polymers.

More generally, the compositions of the invention can comprise all kinds of solid or liquid additives which are known in the art of insecticides and insecticidal treatments.

The surfactants can be of the emulsifying or wetting type, ionic or non-ionic. Possible surfactants are salts of polyacrylic or lignosulfonic acids; salts of phenolsulfonic or naphthalenesulfonic acids; polycondensates of ethylene oxide with fatty alcohols or fatty acids or fatty amines or substituted phenols (particularly alkylphenols or arylphenols); ester-salts of sulfosuccinic acids; taurine derivatives, such as alkyl taurates; phosphoric esters; or esters of alcohols or polyoxyethylated phenols. When the spraying vehicle is water, the use of at least one surfactant is generally required because the active ingredients are not water-soluble.

The method of application of the compositions of the invention is generally the spraying of a mixture which has been previously made, by dilution of more concentrated formulations according to the invention.

Solid compositions can be powders for dusting or for dispersion (wherein the content of active ingredient can be up to 100%) and granules, especially extruded or compacted granules, or granules which have been made by impregnation of a powder (the content of active ingredient in such powders being between about 1 and about 80%).

Liquid compositions or compositions which have to be liquid when applied include solutions, water-soluble concentrates, emulsifiable concentrates, emulsions, wettable powders or pastes or water-dispersible granules.

Emulsifiable concentrates generally comprise from about 10 to about 80% of active ingredient; the emulsions when applied generally comprise from about 0.01 to about 20% of active ingredient.

For example, the emulsifiable concentrates can comprise the solvent and, to the extent needed, from about 2 to about 20% of suitable additives such as stabilizers, surfactants, penetrating agents, corrosion inhibitors or other additives already recited.

These concentrates are usually diluted in tank water so as to obtain the dilution appropriate for spraying.

The concentrated suspensions can also be applied by spraying and have to be fluid without allowing any solid to separate and fall to the bottom. Generally they comprise from about 1 to about 75% of active ingredient (preferably from about 2 to about 50%), from about 0.5 to about 15% of surfactant, from about 0.1 to about 10% of thickener, from 0 to about 10% of other suitable additives as already indicated, the remainder being water or an organic liquid wherein the active ingredient is insoluble or has a low solubility.

The wettable powders generally comprise the active ingredient (from about 1 to about 95%, preferably from about 2 to about 80%), the solid carrier, a wetting agent (from 0 to about 5%), a dispersing agent (from about 3 to about 10%) and, to the extent needed, from 0 to about 10% of other additives such as stabilizers and others as already listed.

In order to obtain these wettable powders or dusting powders, it is appropriate to intimately mix the active ingredients and the additives, as by grinding in a mill or similar device.

Dispersible granules are generally made by agglomeration of a powder, followed by an appropriate granulation process.

The emulsions herein described can be of the oil-in-water or water-in-oil types. Fluidity of the emulsions can range from low viscosities up to high viscosities approaching those of gels.

Among these many compositions or formulations, one skilled in the art can choose the one most appropriate, according to the specific conditions of the treatment problem.

The compounds and compositions of the invention can also be used in admixtures with another pesticide, e.g., an insecticide, acaricide or herbicide.

The compounds of the invention may also be used in controlling pests found in non-agricultural domains.

In the field of veterinary medicine or livestock husbandry or in the maintenance of public health against arthropods, helminths or protozoa which are parasitic internally or externally upon vertebrates, particularly warm-blooded vertebrates, for example man or domestic animals, e.g. cattle, sheep, goats, equines, swine, poultry, dogs or cats, for example Acarina, including ticks (e.g. Ixodes spp., Boophilus spp. e.g. Boophilus microplus, Amblyomma spp., Hyalomma spp., Rhipicephalus spp. e.g. Rhipicephalus appendiculatus, Haemaphysalis spp., Dermacentor spp., Ornithodorus spp. (e.g. Ornithodorus moubata) and mites (e.g. Damalinia spp., Dermahyssus gallinae, Sarcoptes spp. e.g. Sarcoptes scabiei, Psoroptes spp., Chorioptes spp;, Demodex spp., Eutrombicula spp.,); Diptera (e.g. Aedes spp., Anopheles spp., Dermatobia spp., Haematobia spp., Musca spp., Hippoboscidae spp., Hypoderma spp., Gasterophilus spp., Simulium spp); Stomoxys spp., Hemiptera (e.g. Triatoma spp); Phthirapter (e.g. Damalinia spp., Linognathus spp.); Siphonaptera (e.g. Ctenocephalides spp.); Dictyoptera (e.g. Periplaneta spp., Blatella spp.); Hymenoptera (e.g. Monomorium pharaonis); for example against infections of the gastro-intestinal tract caused by parasitic nematode worms, for example members of the family Trichostrongylidae, Nippostrongylus brasiliensis, Trichinella spiralis, Haemonchus contortus, Trichostrongylus colubriformis, Nematodirus batus, Ostertagis circumcincta, Trichostrongylus axei, Cooperia spp. and Hymenolepis nana; in the control and treatment of protozoal diseases caused by, for example, Eimeria spp. e.g. Eimeria tenella, Eimeria acervulina, Eimeria brunetti, Eimeria maxima and Eimeria necatrix, Trypanosoms cruzi, Leishaminia spp., Plasmodium spp., Babesis spp., Trichomonadidae spp., Histomanas spp., Giardia spp., Toxoplasma spp., Entamoeba histolytica and Theileria spp.

Furthermore the compounds of the invention may be useful for coccidiosis, a disease caused by infections from protozoan parasites of the genus Eimeria.

Compositions

Solid or liquid compositions for application topically to animals, timber, stored products or household goods usually contain from about 0.00005% to about 90%, more particularly from about 0.001% to about 10%, by weight of one or more compounds of general formula (I). For administration to animals orally or parenterally, including percutaneously solid or liquid compositions, these normally contain from about 0.1% to about 90% by weight of one or more compounds of general formula (I). Medicated feedstuffs normally contain from about 0.001% to about 3% by weight of one or more compounds of general formula (I). Concentrates or supplements for mixing with feedstuffs normally contain from about 5% to about 90%, preferably from about 5% to about 50%, by weight of one or more compounds of general formula (I). Mineral salt licks normally contain from about 0.1% to about 10% by weight of one or more compounds of general formula (I).

Dusts or liquid compositions for application to livestock, persons, goods, premises or outdoor areas may contain from about 0.0001% to about 15%, more especially from about 0.005% to about 2.0%, by weight, of one or more compounds of general formula (I). Suitable concentrations in treated waters are between about 0.0001 ppm and about 20 ppm, more particularly about 0.001 ppm to about 5.0 ppm of one or more compounds of general formula (I) and may be used therapeutically in fish farming with appropriate exposure times. Edible baits may contain from about 0.01% to about 5%, preferably from about 0.01% to about 1.0%, by weight, of one or more compounds of general formula (I).

When administered to vertebrates parenterally, orally or by percutaneous or other means, the dosage of compounds of general formula (I) will depend upon the species, age, or health of the vertebrate and upon the nature and degree of its actual or potential infestation by arthropod, helminth or protozoan pests. A single dose of about 0.1 to about 100 mg, preferably about 2.0 to about 20.0 mg, per kg body weight of the animal or doses of about 0.01 to about 20.0 mg, preferably about 0.1 to about 5.0 mg, per kg body weight of the animal per day, for sustained medication, are generally suitable by oral or parenteral administration. By use of sustained release formulations or devices, the daily doses required over a period of months may be combined and administered to animals on a single occasion.

The following methods were used to apply the compounds of the invention and to observe the results obtained therewith: a foliar/contact spray on sucking (aphids) or chewing (Lepidoptera) insects.

The species tested were as follows:

    ______________________________________     GENUS, SPECIES     COMMON NAME     ______________________________________     Aphis gossypii     cotton leaf aphid     Musca domestica    housefly     Diabrotica virgifera                        Western cornrootworm     Periplaneta americana                        American Cockroaches     Spodoptera eridania                        Southern armyworm     ______________________________________

The Housefly Bait/Contact Test

About 25 four to six-day-old adult houseflies were anesthetized and placed in a cage with a sugar water bait solution containing the compound. The concentration of the selected compound of formula (I) in the bait solution was 50 ppm. After 24 hours, flies which showed no movement on stimulation were considered dead.

Foliar application (Contact Test) with Aphids

Aphid-infested cotton plants were placed on a revolving turntable, and sprayed to runoff with a 100 ppm formulation of the selected compound of formula (I). The treated, A. gossypii-infested plants were held for three days after treatment, after which the dead aphids were counted.

Application on Western cornrootworm

Jars are filled with 60 g dry soil homogeneously mixed with 5 ml aqueous solution containing the compound to be tested. After drying, four germinated corn seedlings are placed in the bottom of each jar and the soil is wetted. Then ten newly born larvae are placed in each jar. The jars are stored for six days at 27° C. under 70% of relative humidity. The number of surviving larvae are then counted.

Application by contact to Cockroaches

The inner wall of a 100 ml jar is covered by shaking 2 ml of pesticidal formulation. Furthermore, a pellet of dog chow is placed into a jar and the pesticidal formulation is absorbed on the pellet, using excess liquid. The jar is then left open up to evaporation of liquid. Cockroach nymphs are placed in the jar and mortality is assessed after five days.

Application to Southern armyworm

Leaves of soybeans were sprayed to run-off with a spray of various concentrations. Then the leaves were allowed to dry, excised, and placed into a container with five larvae. The containers are stored for five days at 25° C. under 50% relative humidity. Mortality ratings are then counted.

Application to Caenorhabditis elegans (nematode worm)

This test is significative for animal health applications of active ingredient.

Test formulation are prepared by mixing 2 microliters of dimethylsulfoxide with 100 microliters of a solution of Escherichia coli (which is food for C. elegans). 98 microliters of this mixture are then mixed with an inoculum solution which consists of mixed life stages of C. elegans (about 50 worms). This new mixture is stored 7 days at 20° C. Mortality is then visually assessed as well as the behavior of the worm. For the mortality, the rating is either 1 (large increase in number of the population, similar to the control which is trebbling in 7 days) or 3 (slight increase of the population, but significantly less increase than the control) or 5 (little to no increase in the population). For the behavior effect, the rating is either 1 (normal motion) or 3 (motion is slower than the control) or 5 (little to no movement).

All the hereinabove prepared compounds show a positive activity in one or more of these tests (rather good activity on C. elegans).

While the invention has been described in terms of various preferred embodiments, the person skilled in the art will appreciate that various modifications, substitutions, omissions and changes can be made without departing from the spirit thereof. Accordingly, it is intended that the scope of the present invention be limited solely by the scope of the following claims, including equivalents thereof. 

What is claimed is:
 1. A compound of formula (I): ##STR13## wherein: X is N;Y is C--R₃ ; W is C--R₄ ; R₃ is CN; R₄ is --S(O)_(n) R₈ ; R₅ is --NR₉ R₁₀ ; R₈ is alkyl, haloalkyl, alkenyl, or alkynyl, or R₈ is a cycloalkyl ring having 3 to 5 carbon atoms; R₉ and R₁₀, independently of each other, are H, alkyl, haloalkyl, alkylcarbonyl, haloalkylcarbonyl, R₈ S(O)_(n), formyl, alkenyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl, or aroyl, the alkyl portions of R₉ and R₁₀ being optionally substituted by R₇ ; R₇ is cyano, nitro, alkoxy, haloalkoxy, R₈ S(O)_(n), --C(O)alkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, --CO₂ H, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl; Z is C--R₁₆ ; R₁₂, R₁₃, R₁₅ and R₁₆, independently of one another, are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, haloalkylsulfenyl, haloalkylsulfinyl, haloalkylsulfonyl, formyl, alkylcarbonyl or alkoxycarbonyl; R₂₂, R₂₃, R₂₄, R₂₅, and R₂₆, independently of one another, are halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, haloalkylcarbonyl, formyl, alkylcarbonyl, thioamide, amide, alkoxycarbonyl, SF₅, or R₈ S(O)_(n) ;or a pesticidally acceptable salt thereof.
 2. A compound according to claim 1, wherein R₂₄ is halogen, haloalkyl or haloalkoxy.
 3. A compound according to claim 1, wherein R₅ is --NH₂.
 4. A compound according to claim 1, wherein R₈ is lower alkyl or haloalkyl.
 5. A compound according to claim 1, having at least one feature selected from the group consisting of:R₈ is methyl, ethyl, --CF₃, --CFCl₂, or --CF₂ Cl; R₁₂ and R₁₆, independently of each other, are F, Cl, Br or H; R₁₃ and R₁₅ are H; R₂₄ is --CF₃, --OCF₃, --CHF₂, --S(O)_(n) CF₃, --CFCl₂, --CF₂ Cl, --OCF₂ Cl, --OCFCl₂, Cl, Br or F; and Z is CCl, CF, or CBr.
 6. A compound according to claim 2, wherein R₅ is --NH₂.
 7. A compound according to claim 1, wherein:R₁₂ and R₁₆, independently of each other, are Cl or Br; R₁₃ and R₁₅ are H; R₂₄ is --CF₃, --OCF₃ or Br; R₅ is amino; R₉ and R₁₀, independently of each other, are H, alkyl or alkylcarbonyl; and R₈ is methyl, ethyl, CF₃, CFCl₂ or CF₂ Cl.
 8. A compound according to claim 2, wherein:R₁₂ and R₁₆, independently of each other, are Cl or Br; R₂₄ is --CF₃, --OCF₃ or Br; R₅ is amino; and R₉ and R₁₀, independently of each other, are H, alkyl or alkylcarbonyl.
 9. A compound according to claim 1, wherein the S(O)_(n) R₈ substituent of formula (I) is: methylthio, methylsulfinyl, methylsulfonyl, ethylsulfinyl, ethylsulfonyl, ethylthio, cyclopropylsulfinyl, cyclopropylthio, cyclopropylsulfonyl, isopropylsulfinyl, isopropylsulfonyl, isopropylthio, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, dichlorofluoromethylthio, dichlorofluoromethylsulfinyl, dichlorofluoromethylsulfonyl, chlorodifluoromethylthio, chlorodifluoromethylsulfonyl or chlorodifluoromethylsulfinyl.
 10. A compound according to claim 5, wherein the S(O)_(n) R₈ substituent of formula (I) is: trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, dichlorofluoromethylthio, dichlorofluoromethylsulfinyl, dichlorofluoromethylsulfonyl, chlorodifluoromethylthio, chlorodifluoromethylsulfonyl or chlorodifluoromethylsulfinyl.
 11. A compound according to claim 7, wherein the S(O)_(n) R₈ substituent of formula (I) is: trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, dichlorofluoromethylthio, dichlorofluoromethylsulfinyl, dichlorofluoromethylsulfonyl, chlorodifluoromethylthio, chlorodifluoromethylsulfonyl or chlorodifluoromethylsulfinyl.
 12. A compound according to claim 8, wherein the S(O)_(n) R₈ substituent of formula (I) is: trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, dichlorofluoromethylthio, dichlorofluoromethylsulfinyl, dichlorofluoromethylsulfonyl, chlorodifluoromethylthio, chlorodifluoromethylsulfonyl or chlorodifluoromethylsulfinyl.
 13. The compound of formula (I) according to claim 1, which is:1- 2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl!-3-cyano-4-trifluoromethylthio-5-aminopyrazole; or 1- 2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl!-3-cyano-4-trifluoromethylsulfonyl-5-aminopyrazole.
 14. A pesticidal composition comprising:(a) a pesticidally effective amount of a compound of formula (I): ##STR14## wherein: X is N; Y is C--R₃ ; W is C--R₄ ; R₃ is CN; R₄ is --S(O)_(n) R₈ ; R₅ is --NR₉ R₁₀ ; R₈ is alkyl, haloalkyl, alkenyl, or alkynyl, or R₈ is a cycloalkyl ring having 3 to 5 carbon atoms; R₉ and R₁₀, independently of each other, are H, alkyl, haloalkyl, alkylcarbonyl, haloalkylcarbonyl, R₈ S(O)_(n), formyl, alkenyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl, or aroyl, the alkyl portions of R₉ and R₁₀ being optionally substituted by R₇ ; R₇ is cyano, nitro, alkoxy, haloalkoxy, R₈ S(O)_(n), --C(O)alkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, --CO₂ H, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl; Z is C--R₁₆ ; R₁₂, R₁₃, R₁₅ and R₁₆, independently of one another, are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, haloalkylsulfenyl, haloalkylsulfinyl, haloalkylsulfonyl, formyl, alkylcarbonyl or alkoxycarbonyl; R₂₂, R₂₃, R₂₄, R₂₅, and R₂₆, independently of one another, are halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, haloalkylcarbonyl, formyl, alkylcarbonyl, thioamide, amide, alkoxycarbonyl, SF₅, or R₈ S(O)_(n) ;or a pesticidally acceptable salt thereof; and (b) a pesticidally acceptable carrier therefor.
 15. A composition according to claim 14, comprising from 0.001 to 95% of compound of formula (I).
 16. A method for controlling pests at a locus comprising applying to said locus a pesticidally effective amount of a compound of formula (I): ##STR15## wherein: X is N;Y is C--R₃ ; W is C--R₄ ; R₃ is H, halogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, haloalkoxy, CN; R₄ is --S(O)_(n) R₈ ; R₅ is --NR₉ R₁₀ ; R₈ is alkyl, haloalkyl, alkenyl, or alkynyl, or R₈ is a cycloalkyl ring having 3 to 5 carbon atoms; R₉ and R₁₀, independently of each other, are H, alkyl, haloalkyl, alkylcarbonyl, haloalkylcarbonyl, R₈ S(O)_(n), formyl, alkenyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl, or aroyl, the alkyl portions of R₉ and R₁₀ being optionally substituted by R₇ ; R₇ is cyano, nitro, alkoxy, haloalkoxy, R₈ S(O)_(n), --C(O)alkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, --CO₂ H, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl; Z is C--R₁₆ ; R₁₂, R₁₃, R₁₅ and R₁₆, independently of one another, are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, haloalkylsulfenyl, haloalkylsulfinyl, haloalkylsulfonyl, formyl, alkylcarbonyl or alkoxycarbonyl; R₂₂, R₂₃, R₂₄, R₂₅, and R₂₆, independently of one another, are halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, haloalkylcarbonyl, formyl, alkylcarbonyl, thioamide, amide, alkoxycarbonyl, SF₅, or R₈ S(O)_(n) ;or a pesticidally acceptable salt thereof.
 17. A method according to claim 16, wherein said pests are insects and wherein said pesticidally effective amount is an insecticidally effective amount.
 18. A method according to claim 17, comprising applying to said locus from about 0.01 to about 2 kg/ha of compound of formula (I).
 19. A method according to claim 18, comprising applying to said locus from about 0.1 to about 1 kg/ha of compound of formula (I).
 20. A method for controlling pests at a locus comprising applying to said locus a pesticidally effective amount of a composition as claimed in claim
 14. 21. A method according to claim 20, wherein said pests are insects and wherein said pesticidally effective amount is an insecticidally effective amount. 